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WO2010016127A1 - Additif pour fluide de lubrification, composition de fluide de lubrification et procédé pour la fabrication d'une polyoléfine soufrée - Google Patents

Additif pour fluide de lubrification, composition de fluide de lubrification et procédé pour la fabrication d'une polyoléfine soufrée Download PDF

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Publication number
WO2010016127A1
WO2010016127A1 PCT/JP2008/064213 JP2008064213W WO2010016127A1 WO 2010016127 A1 WO2010016127 A1 WO 2010016127A1 JP 2008064213 W JP2008064213 W JP 2008064213W WO 2010016127 A1 WO2010016127 A1 WO 2010016127A1
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WIPO (PCT)
Prior art keywords
sulfurized olefin
sulfur
lubricating fluid
hydrogen sulfide
dienes
Prior art date
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Ceased
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PCT/JP2008/064213
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English (en)
Japanese (ja)
Inventor
滋 山田
周次郎 大槻
浩 坂田
ゾンカ チェン
シャオジン スン
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DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to PCT/JP2008/064213 priority Critical patent/WO2010016127A1/fr
Publication of WO2010016127A1 publication Critical patent/WO2010016127A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
    • C10M151/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/41—Chlorine free or low chlorine content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/70—Soluble oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/10—Chemical after-treatment of the constituents of the lubricating composition by sulfur or a compound containing sulfur

Definitions

  • the present invention has a high sulfur content, a load resistance performance and oxidation stability when used as an extreme pressure additive, and a non-chlorine additive for lubricating fluids that is excellent in non-ferrous metal low corrosion resistance.
  • the present invention relates to a lubricating fluid composition used and a method for producing a sulfurized olefin useful as an additive for the lubricating fluid.
  • sulfurized olefins are blended with base oils such as mineral oils and synthetic oils, so that cutting oils, plastic working oils, gear oils, sliding surface oils used to prevent friction between metals, wear reduction and seizure are used. It is widely used as an extreme pressure additive for lubricating fluids such as grease.
  • a method for producing a sulfurized olefin used for such applications for example, a method in which an adduct obtained by reacting an aliphatic monoolefin and sulfur chloride is further reacted with mercaptanoic acid / polysulfide is proposed.
  • the sulfurized olefin obtained by this method contains chlorine derived from the raw material, and the chlorine is a cause of rusting of the target metal or is released to the environment, and therefore, improvement is required. It has been.
  • the production method described in Patent Document 1 has a problem in that the yield is low and a large amount of water is required in the product purification (dechlorination) step.
  • the sulfurized olefin described in Patent Document 2 has a dialkyl polysulfide structure.
  • a sulfurized olefin composition excellent in so-called extreme pressure performance that prevents friction between the metals described above, wear reduction, and seizure it is necessary to use a sulfurized olefin having a high sulfur content.
  • the sulfur bridge length (as used herein, the term “sulfur bridge length” refers to “the average number of sulfur atoms per mono- and polysulfide bond contained in the molecule”.
  • the present invention was invented in view of the above situation, and its purpose was to have a high sulfur content, good load bearing performance and good oxidation stability when used as an extreme pressure additive, and low non-ferrous metal corrosion.
  • An object of the present invention is to provide a non-chlorine-based additive for lubricating fluid that is excellent in properties.
  • Another object of the present invention is to provide a non-chlorine-based lubricating fluid composition to which such an additive for lubricating fluid is added, has good load bearing performance and oxidation stability, and is excellent in non-ferrous metal low corrosion resistance. It is in.
  • Another object of the present invention is to provide a method for producing a sulfurized olefin useful as an additive for such a lubricating fluid.
  • the present inventors have found that the average number of sulfur atoms per mono- and polysulfide bond contained in the molecule is 1 to 3, making it difficult for the sulfur atoms to become free (active).
  • the above-mentioned problem can be solved by using a sulfurized olefin (A) substantially free of chlorine and having a sulfur content in the molecule of 40 to 55% by weight as an additive for lubricating fluid.
  • a sulfurized olefin (A) can be produced by reacting dienes, sulfur, and hydrogen sulfide, and have completed the present invention based on these findings.
  • the present invention is substantially free of chlorine, wherein the average number of sulfur atoms per mono- and polysulfide bond contained in the molecule is 1-3 and the sulfur content in the molecule is 40-55 wt%.
  • an additive for a lubricating fluid characterized by comprising a sulfurized olefin (A).
  • the present invention also provides a lubricating fluid composition comprising a sulfurized olefin (A) and a base oil (B).
  • the present invention provides a method for producing a sulfurized olefin characterized by producing a sulfurized olefin (A) by reacting dienes (a1), sulfur (a2) and hydrogen sulfide (a3).
  • the present invention provides a sulfur atom per average mono- and polysulfide bond contained in a molecule obtained by reacting a mixture of two or more types of dienes (a1), sulfur (a2) and hydrogen sulfide (a3).
  • a sulfurized olefin substantially free of chlorine having a number of 1-3 and a sulfur content in the molecule of 40-55 wt%.
  • the additive for lubricating fluids of the present invention has a high sulfur content, so it has good load-bearing performance and oxidation stability when used as an extreme pressure additive, and is substantially free of chlorine because it contains substantially no chlorine. Excellent.
  • the lubricating fluid composition of the present invention contains the lubricating fluid additive in the base oil, the load bearing performance and oxidation stability are good, and the non-ferrous metal has low corrosion resistance.
  • a sulfurized olefin useful as an additive for a lubricating fluid can be synthesized in a high yield by the reaction of dienes, sulfur and hydrogen sulfide.
  • the additive for lubricating fluid of the present invention substantially contains chlorine having 1 to 3 sulfur atoms per average mono- and polysulfide bond contained in the molecule and a sulfur content of 40 to 55% by weight in the molecule. It is made of a sulfurized olefin (hereinafter referred to as “sulfurized olefin (A)”) which is not contained.
  • the sulfurized olefin (A) is a general example of the general formula (1).
  • R 1 S- (S x -R 2 -S y ) n -R 1 (1) (Wherein x represents 0 or an integer of 1 to 2, y represents an integer of 1 to 3, n represents an integer of 1 to 10, and R 1 and R 2 each represent a monovalent or 2 having 4 to 10 carbon atoms. Represents a valent alkyl group or an alkenyl group.)
  • the sulfurized olefin represented by these is included.
  • the sulfur content of the sulfurized olefin (A) is 42 to 52% by weight from the viewpoint of excellent load bearing performance of the lubricating fluid composition when used as an additive for lubricating fluid such as an extreme pressure additive. Particularly preferred is 44 to 50% by weight.
  • the viscosity of the sulfurized olefin (A), excellent compatibility with later-described base oil (B), from the point it is easy to handle, with a kinematic viscosity criteria at 40 ° C. usually 10 ⁇ 1,500mm 2 / s, preferably 100 to 1,000 mm 2 / s, particularly preferably 100 to 400 mm 2 / s.
  • the molecular weight of the sulfurized olefin (A) is not particularly limited, the oligomer has a good balance of compatibility with the base oil (B), load resistance, and low corrosiveness to non-ferrous metals.
  • the distribution of the sulfurized olefin (A) according to the degree of polymerization is preferably such that the total content of dimerized to 7-mer sulfurized olefins contained in 100 moles of the sulfurized olefin (A) is 55 moles or more. It is preferably ⁇ 70 mol.
  • the distribution of the sulfurized olefin (A) depending on the degree of polymerization can be obtained from a GPC chart attached as a drawing.
  • the sulfurized olefin (A) can be produced by reacting dienes (a1), sulfur (a2) and hydrogen sulfide (a3). At this time, the sulfurized olefin (A) is preferably produced by reacting a mixture of two or more dienes (a1), sulfur (a2) and hydrogen sulfide (a3).
  • dienes having 4 to 10 carbon atoms are preferable.
  • 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene (piperylene), cyclopentadiene, 1,5-hexadiene, cyclohexadiene, 1,6-heptadiene, cyclohepta Examples include diene, 1,7-octadiene, cyclooctadiene, and the like. These may be used alone or in combination of two or more.
  • dienes having 4 to 6 carbon atoms are preferably used.
  • 1,3-butadiene, 2-methyl-1,3 -It is preferable to use butadiene (isoprene), 1,3-pentadiene (piperylene), cyclopentadiene, 1,5-hexadiene or cyclohexadiene.
  • 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene) from the viewpoint of excellent balance between the sulfur content of the obtained sulfurized olefin and the compatibility with the base oil.
  • 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene) and dicyclopentadiene are used because of the excellent balance between the sulfur content of the resulting sulfurized olefin and the compatibility with the base oil. Most preferred.
  • the blending ratio of the dienes having these properties is not particularly limited. However, when 1,3-butadiene is combined with 2-methyl-1,3-butadiene (isoprene), 0.5 to 10.0. The oil solubility and the fusion load are improved even when the amount of 2-methyl-1,3-butadiene (isoprene) is added by weight%. In addition, even when 1,3-butadiene is added to 2-methyl-1,3-butadiene (isoprene), oxidation stability and resistance are improved even when 1,3-butadiene is added in an amount of 0.5 to 10.0% by weight. Copper plate corrosivity is improved. Further, in any case of 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene), the oxidation stability is improved even when the amount of dicyclopentadiene added is 0.5 to 10.0% by weight.
  • the sulfur (a2) is not particularly limited, and it may be in the form of a small lump, flake, powder, or a molten state (liquid), but the number of carbon atoms used is 4 Dienes of 6 to 6 have a low boiling point, avoiding dangers due to a sudden increase in pressure in the reaction vessel due to mixing of the dienes and molten sulfur (130 ° C.) in the reaction vessel and an increase in internal temperature, side reactions, etc. In order to prevent, the use of solid sulfur is preferred. Since there is a high risk of dust explosion caused by dust generated when powdered sulfur is added, a small lump or flake shape is more preferable.
  • the hydrogen sulfide (a3) is not particularly limited, but it is preferable to use one having a purity of 99 mol% or more from the viewpoint of obtaining a high-purity sulfurized olefin.
  • the sulfur (a2) is not particularly limited, and may be in a solid state such as a small lump, flake, or powder, or in a molten state (liquid).
  • molten sulfur when molten sulfur is used, it is preferable to add it in a molten state at 125 to 155 ° C., since the viscosity is low and constant.
  • the dienes having 4 to 6 carbon atoms to be used have a low boiling point, and the pressure in the reaction vessel is rapidly increased and the internal temperature is increased by mixing the dienes with molten sulfur (for example, 125 to 155 ° C.) in the reaction vessel.
  • Use of solid sulfur is preferred when it is necessary to avoid danger due to the rise and prevent side reactions. Since there is a high risk of dust explosion caused by dust generated when powdered sulfur is added, a small lump or flake shape is more preferable.
  • the monoolefins are not particularly limited, and examples thereof include isobutylene, 2-methyl-2-pentene, 2-methyl-2-butene, 2-methyl-1-butene, diisobutylene, triisobutylene, and triisobutylene.
  • Examples include chain alkenes such as propylene, 1-hexene, 1-octene, 1-nonene, 1-dodecene and 1-hexadecene, and cyclic alkenes such as cyclopentene and cyclohexene. These can also be used as a mixture. it can.
  • the amine catalyst (a4) that can be used here is not particularly limited and may be either an aliphatic amine or an aromatic amine.
  • N-methylpiperazine N-methylpiperazine, morpholy 1,4-bis- (8-aminopropyl) -piperazine, piperazine-1,4-diazacycloheptane, 1- (2'-aminoethylpiperazine), 1- [2 '-(2 "-amino Ethylamino) ethyl] piperazine, 1,11-diazacycloeicosane, 1,15-diazacyclooctacosane and the like, and these can be used alone or as a mixture of two or more.
  • dibutylamine, dicyclohexylamine octylamine, dioctylamine, and various isomers thereof from the viewpoint that the yield of sulfurized olefin is high and can be separated and removed from the composition by a simple method such as distillation or aeration after the reaction.
  • Dodecylamine, tetradecylamine, hexadecylamine, dicyclohexylamine, and various isomers thereof are preferably used.
  • the amount of the amine catalyst (a4) to be used is appropriately selected depending on the desired reaction rate, but it is preferably a small amount within a range in which the reactivity is not deteriorated. 0.05 to 1.5% by weight, particularly preferably 0.5 to 0.8% by weight.
  • a pressure reaction vessel is charged with dienes (a1), sulfur (a2), amine-based catalyst (a4) and hydrogen sulfide (a3) at a temperature of 0 to 40 ° C., sealed and heated to 50 to 90 ° C. for reaction.
  • diene (a1), sulfur (a2), and amine catalyst (a4) are charged into a pressurized reaction vessel and sealed, and then the hydrogen sulfide (a3) gas is heated to 50 to 120 ° C., preferably 60 to 90 ° C.
  • a method of blowing at °C may be used.
  • the temperature is too low, it takes a long reaction time, and if the temperature is too high, the polycondensation reaction of the dienes (a1) having a competitive reaction with the sulfur crosslinking reaction is likely to occur. ) May be reduced in the base oil (B), and the hue and odor may be deteriorated. It is preferable to appropriately set the temperature depending on the performance of the intended additive for lubricating fluid and the lubricating fluid composition, the desired production time, and the like.
  • the above-mentioned hydrogen sulfide (a3) blowing time is not particularly limited, but is usually 5 to 100 hours, preferably 5 to 50 hours. After completion of the blowing, the pressure is returned to normal pressure, and the unreacted diene (a1) and the remaining hydrogen sulfide (a3) are distilled off to obtain the target sulfurized olefin (A).
  • the obtained sulfurized olefin (A) can be used alone or in combination of two or more for the lubricating fluid additive or lubricating fluid composition of the present invention.
  • the use of the sulfurized olefin of the present invention is not particularly limited.
  • it can be added to a base oil as a lubricating fluid additive and used as a lubricant composition, and can be used as an internal combustion engine, an automatic transmission, a buffer.
  • Power transmission in hydraulic systems such as motors, power steering and other drive system equipment, automotive lubricating oils used in gears, metal working oils used in metal working such as cutting, grinding and plastic working, hydraulic equipment and devices It can be used as hydraulic fluid that is a power transmission fluid used for operations such as force control and buffering.
  • the sulfurized olefin composition of the present invention can reduce the degree of swelling of a gearbox used in gear oil sealant (chloroprene rubber, nitrile rubber, etc.) as compared with conventional products, It can also be suitably used for applications that come into contact with the agent.
  • the lubricating fluid composition of the present invention comprises a sulfurized olefin (A) and a base oil (B).
  • the base oil (B) used in the present invention is not limited in any way, and can be appropriately selected from mineral oil, synthetic oil, etc. according to the purpose of use and conditions of use.
  • the mineral oil include, for example, distillate obtained by subjecting paraffin-based crude oil, intermediate-based crude oil, and naphthene-based crude oil to atmospheric distillation or vacuum distillation of the residue after atmospheric distillation, or solvent purification, water
  • Examples include refined oils obtained by refining such as refining, dewaxing, and clay treatment.
  • Examples of the synthetic oil include polyols such as low molecular weight polybutene, low molecular weight polypropylene, ⁇ -olefin oligomers having 8 to 14 carbon atoms and hydrides thereof, trimethylolpropane fatty acid ester, pentaerythritol fatty acid ester, and the like.
  • Examples include esters, dibasic acid esters, aromatic polycarboxylic acid esters, ester compounds such as phosphate esters, alkylaromatic compounds such as alkylbenzene and alkylnaphthalene, polyglycol oils such as polyalkylene glycol, silicone oils, and the like. These can be used alone or in combination of two or more.
  • the blending ratio of the sulfurized olefin (A) and the base oil (B) in the lubricating fluid composition of the present invention is not particularly limited, but is usually sulfurized with respect to 100 parts by weight of the base oil (B).
  • the olefin (A) is 0.01 to 50 parts by weight, preferably 0.05 to 10 parts by weight.
  • the lubricating fluid composition of the present invention can be used as grease by further adding a thickener (C) to the sulfurized olefin (A) and the base oil (B).
  • a thickener (C) that can be used here include soaps such as metal soaps and composite soaps, or ureas.
  • soaps such as metal soaps and composite soaps, or ureas.
  • the lubricating fluid composition of the present invention is not limited except that the sulfurized olefin (A) and the base oil (B) are used.
  • an oily agent an antiwear agent, an extreme pressure Agents, other rust inhibitors, corrosion inhibitors, antifoaming agents, cleaning dispersants, pour point depressants, viscosity index improvers, antioxidants, emulsifiers, demulsifiers, antifungal agents, friction modifiers, surfactants
  • an additives can be appropriately used in accordance with the intended use and performance.
  • Oil-based agents include long-chain fatty acids (oleic acid), anti-wear agents such as phosphate esters and metal dithiophosphate salts; extreme pressure agents such as organic sulfur compounds and organic halogen compounds, and other rust inhibitors Carboxylic acids, amines, alcohols, esters, etc .; as corrosion inhibitors, nitrogen compounds (benzotriazole, etc.), sulfur and nitrogen containing compounds (1,3,4-thiadiazolyl-2,5-bisdialkyldithiocarbamate), etc .; Silicone oil, metal soap, fatty acid ester, phosphate ester, etc.
  • foaming agent neutral and basic sulfonate and phenate (metal salt type), succinimide, ester, benzylamine copolymer polymer, etc. as cleaning dispersant ;
  • Pour point depressants include chlorinated paraffin and naphthalene or phenol.
  • the lubricating fluid composition of the present invention is one in which the sulfurized olefin (A), the base oil (B), and a thickener (C) and other additives that are blended as necessary are uniformly blended.
  • the blending method is not particularly limited, and at this time, it can be heated to 30 to 60 ° C. for homogenization.
  • the lubricating fluid composition of the present invention is not particularly limited.
  • the lubricating fluid composition can be used as a lubricant composition, and can be used as a drive system device such as an internal combustion engine, an automatic transmission, a shock absorber, or power steering.
  • the lubricating fluid composition of the present invention can reduce the degree of swelling of a gearbox used in gear oil sealant (chloroprene rubber, nitrile rubber, etc.) as compared with conventional products. It can also be suitably used for applications that come into contact with the agent.
  • gear oil sealant chloroprene rubber, nitrile rubber, etc.
  • Oxidation stability test (ISOT test): The test was performed according to JIS K-2514.4. Sample addition amount: 4% Conditions: 135 ° C., 96 hours Base oil: 500 neutral oil (100 mm 2 / s at 40 ° C.)
  • Copper plate corrosivity test Executed according to JIS K-2513. Sample addition amount: 5% Base oil: 500 neutral oil (100 cSt at 40 ° C) Temperature: 100 ° C Time: 1 hour or 3 hours
  • Example 1 (Isoprene sulfide) In a 1 liter autoclave equipped with a heating device, a hydrogen sulfide blowing tube and a hydrogen sulfide absorption device, 476 g (7.0 mol) of isoprene, 179 g (5.6 mol) of powdered sulfur, and 6.3 g of dibutylamine as a catalyst. Prepared. After sealing the autoclave, it was heated until the internal temperature reached 85 ° C. 190 g (5.6 mol) of hydrogen sulfide gas (purity 99.9 mol%) was blown in at a pressure of 6 kg / cm 2 for 20 hours. Furthermore, it was kept at the same temperature for 48 hours.
  • Example 2 (sulfur butadiene) A 1 liter autoclave equipped with a warming device, a hydrogen sulfide blowing tube and a hydrogen sulfide absorption device was charged with 179 g (5.6 mol) of powdered sulfur and 6.3 g of dibutylamine as a catalyst. After the autoclave was sealed, the inside of the reaction vessel was depressurized to ⁇ 0.1 MPa or less using a vacuum pump and vacuum deaerated. Thereafter, the 1,3-butadiene cylinder was connected to an autoclave, and 378 g (7.0 mol) of 1,3-butadiene was charged. The internal temperature was increased to 85 ° C.
  • the sulfurized olefin (A-2) obtained had a sulfur crosslink length of 2.32, a sulfur content of 49%, a number average molecular weight of 607, a kinematic viscosity at 40 ° C. of 198.5 mm 2 / s, The total content of dimer to heptamer was 60 mol.
  • the GPC chart of the resulting sulfurized olefin (A-2) is shown in FIG. 3, and the 13 C-NMR chart is shown in FIG.
  • Example 3 (sulfurized isoprene-butadiene) In a 1 liter autoclave equipped with a heating device, a hydrogen sulfide blowing tube and a hydrogen sulfide absorption device, 452 g (6.65 mol) of isoprene, 179 g (5.6 mol) of powdered sulfur, and 6.3 g of dibutylamine as a catalyst. Prepared. After the autoclave was sealed, the inside of the reaction vessel was depressurized to ⁇ 0.1 MPa or less using a vacuum pump and vacuum deaerated. Thereafter, the 1,3-butadiene cylinder was connected to an autoclave, and 18.9 g (0.35 mol) of 1,3-butadiene was charged.
  • Example 4 (sulfurized isoprene-dicyclopentadiene)
  • a heating device a hydrogen sulfide blowing tube and a hydrogen sulfide absorption device
  • 452 g (6.65 mol) of isoprene 46.2 g (0.35 mol) of dicyclopentadiene
  • 179 g of powdered sulfur 5.6 mol
  • 6.3 g of dibutylamine as a catalyst.
  • Example 5 (sulfur butadiene-isoprene) In a 1 liter autoclave equipped with a heating device, a hydrogen sulfide blowing tube and a hydrogen sulfide absorption device, 23.8 g (0.35 mol) of isoprene, 179 g (5.6 mol) of powdered sulfur, and dibutylamine 6 as a catalyst .3 g was charged. After the autoclave was sealed, the inside of the reaction vessel was depressurized to ⁇ 0.1 MPa or less using a vacuum pump and vacuum deaerated. Thereafter, the 1,3-butadiene cylinder was connected to an autoclave, and 359 g (6.65 mol) of 1,3-butadiene was charged.
  • the internal temperature was increased to 85 ° C.
  • 190 g (5.6 mol) of hydrogen sulfide gas (purity 99.9 mol%) was blown in at a pressure of 6 kg / cm 2 for 20 hours. Furthermore, it was kept at the same temperature for 48 hours. Then, after cooling to 40 ° C., the valve connected to the hydrogen sulfide absorber is opened to return the pressure to normal pressure, air is blown from the blowing pipe, and the remaining hydrogen sulfide and unreacted isoprene are distilled off.
  • 720 g (yield 95%) of sulfurized olefin (A-3) was obtained.
  • the sulfurized olefin (A-3) obtained had a sulfur content of 48%, a number average molecular weight of 546, and a kinematic viscosity at 40 ° C. of 100.5 mm 2 / s.
  • Example 6 (sulfur butadiene dicyclopentadiene)
  • a heating device a hydrogen sulfide blowing tube and a hydrogen sulfide absorption device
  • 46.2 g (0.35 mol) of dicyclopentadiene 179 g (5.6 mol) of powdered sulfur
  • 6.3 g of butylamine was charged.
  • the inside of the reaction vessel was depressurized to ⁇ 0.1 MPa or less using a vacuum pump and vacuum deaerated.
  • the 1,3-butadiene cylinder was connected to an autoclave, and 359 g (6.65 mol) of 1,3-butadiene was charged.
  • the internal temperature was increased to 85 ° C. 190 g (5.6 mol) of hydrogen sulfide gas (purity 99.9 mol%) was blown in at a pressure of 6 kg / cm 2 for 20 hours. Furthermore, it was kept at the same temperature for 48 hours. Then, after cooling to 40 ° C., the valve connected to the hydrogen sulfide absorber is opened to return the pressure to normal pressure, air is blown from the blowing pipe, and the remaining hydrogen sulfide and unreacted isoprene are distilled off. 741 g (yield 95%) of sulfurized olefin (A-3) was obtained. The sulfurized olefin (A-4) obtained had a sulfur content of 47%, a number average molecular weight of 774, and a kinematic viscosity at 40 ° C. of 126.6 mm 2 / s.
  • Comparative Example 1 (sulfurized isobutylene) In a 50 ml autoclave equipped with a heating device and a hydrogen sulfide absorption device, 3.2 g (0.1 mol) of powdered sulfur and 0.021 g of dicyclohexylamine as a catalyst were charged. Thereafter, the isobutylene cylinder was connected to an autoclave, and 3.03 g (0.05 mol) of isobutylene was charged. The internal temperature was increased to 85 ° C. Hydrogen sulfide gas (purity 99.9 mol%) 0.96 g (0.03 mol) was blown into it at a pressure of 6 kg / cm 2 over time. Furthermore, it was kept at the same temperature for a time.
  • Comparative example 2 (sulfur diisobutylene)
  • a heating device equipped with a heating device, a hydrogen sulfide blowing tube and a hydrogen sulfide absorption device
  • 786 g (7.0 mol) of diisobutylene 786 g (7.0 mol) of diisobutylene
  • 379 g (11.8 mol) of sulfur powder and 2.3 g of dicyclohexylamine as a catalyst.
  • 129 g (3.8 mol) of hydrogen sulfide gas purity 99.9 mol%) was blown in at a pressure of 6 kg / cm 2 for 20 hours. Furthermore, it was kept at the same temperature for 1 hour.
  • Physical property comparison Table 1 shows the physical property values (sulfur bridge length, sulfur content, color, number average molecular weight, and kinematic viscosity) of each sulfurized olefin obtained in Examples 1 and 2 and Comparative Examples 1 and 2, and GPC analysis. Based on the molecular weight distribution obtained, the calculated values of the component content of each composition from the monomer to the heptamer are shown in Table 2.
  • Table 3 shows the results of the extreme pressure performance test (high-speed 4-ball test), the oxidation stability test (ISOT test) and the copper plate corrosion test of the sulfurized olefin composition.
  • the copper plate corrosion test results in Table 3 are based on the ASTM standard.
  • the evaluation rank is 12 ranks of 1a, 1b, 2a, 2b, 2c, 2d, 2e, 3a, 3b, 4a, 4b, 4c, 1a is the least corrosive, 4c is the most corrosive, and ascending from 1a It shows that the corrosivity becomes large.
  • the lubricating fluid composition (sulfurized olefin composition) of the present invention is substantially equivalent to that of the comparative example in each test item of the high-speed four-ball test and the ISOT test. It can be seen that the copper plate corrosion test shows significantly better corrosion resistance than that of the comparative example.
  • Table 3 shows the results of the extreme pressure performance test (high-speed 4-ball test), the oxidation stability test (ISOT test) and the copper plate corrosion test of the sulfurized olefin composition.
  • Example 1 is a GPC chart of sulfurized olefin obtained in Example 1.
  • 3 is a 13 C-NMR spectrum of the sulfurized olefin obtained in Example 1.
  • 2 is a GPC chart of sulfurized olefin obtained in Example 2.
  • 3 is a 13 C-NMR spectrum of the sulfurized olefin obtained in Example 2.
  • 2 is a GPC chart of sulfurized olefin obtained in Comparative Example 1.
  • 3 is a 13 C-NMR spectrum of a sulfurized olefin obtained in Comparative Example 1.
  • 4 is a GPC chart of sulfurized olefin obtained in Comparative Example 2.
  • 3 is a 13 C-NMR spectrum of a sulfurized olefin obtained in Comparative Example 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Abstract

L'invention a pour objet une oléfine soufrée sans chlore qui a une viscosité appropriée et une solubilité dans une huile de base appropriée, une teneur en soufre élevée, une bonne propriété de résistance aux charges et une bonne stabilité à l'oxydation lorsqu'elle est utilisée comme additif extrême-pression et qui est excellente en termes de faible corrosivité vis-à-vis de métaux non ferreux; une oléfine soufrée sans chlore qui a une bonne propriété de résistance aux charges et une bonne stabilité à l'oxydation et qui est excellente en termes de faible corrosivité vis-à-vis de métaux non ferreux; et un procédé pour la fabrication de l'oléfine soufrée. L'invention porte sur un procédé pour la fabrication d'une oléfine soufrée (A) comprenant la réaction d'au moins deux types de diènes (a1), de soufre (a2), de sulfure d'hydrogène (a3) et d'une amine (a4) les uns avec les autres pour obtenir l'oléfine soufrée (A); et sur l'oléfine soufrée contenant 1 à 3 atomes de soufre en moyenne par liaison monosulfure et liaison polysulfure dans une molécule, ayant une teneur en soufre de 40 à 55 % en poids dans la molécule et ne contenant pratiquement pas de chlore obtenue par la réaction d'un mélange de deux ou plus de deux types de diènes (a1), de soufre (a2) et de sulfure d'hydrogène (a3) les uns avec les autres.
PCT/JP2008/064213 2008-08-07 2008-08-07 Additif pour fluide de lubrification, composition de fluide de lubrification et procédé pour la fabrication d'une polyoléfine soufrée Ceased WO2010016127A1 (fr)

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WO2016138407A1 (fr) 2015-02-27 2016-09-01 Cargill, Incorporated Huiles polymérisées et leur procédés de fabrication
US10316192B2 (en) 2017-08-25 2019-06-11 Cargill, Incorporated Emulsions with polymerized oils and methods of manufacturing the same
US11390873B2 (en) 2011-01-25 2022-07-19 Cargill, Incorporated Compositions and methods for succinate production
CN116925831A (zh) * 2022-11-30 2023-10-24 世名(苏州)新材料研究院有限公司 一种硫化烯烃及其制备方法和应用

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JP2008222997A (ja) * 2007-02-14 2008-09-25 Dic Corp 潤滑流体用添加剤、潤滑流体組成物及び硫化ポリオレフィンの製造方法

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JPS5352510A (en) * 1976-09-24 1978-05-13 Cooper & Co Ltd Edwin Additive for lubricating oil and lubricating oil added it and its preparation
JP2007191522A (ja) * 2006-01-17 2007-08-02 Dainippon Ink & Chem Inc 潤滑流体用添加剤、潤滑流体組成物及び硫化ポリオレフィンの製造方法
JP2008222997A (ja) * 2007-02-14 2008-09-25 Dic Corp 潤滑流体用添加剤、潤滑流体組成物及び硫化ポリオレフィンの製造方法

Cited By (15)

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Publication number Priority date Publication date Assignee Title
US11390873B2 (en) 2011-01-25 2022-07-19 Cargill, Incorporated Compositions and methods for succinate production
US11898037B2 (en) 2015-02-27 2024-02-13 Cargill, Incorporated Rejuvenating compositions for asphalt applications and methods of manufacturing the same
US11905415B2 (en) 2015-02-27 2024-02-20 Cargill, Incorporated Polymerized oils and methods of manufacturing the same
US12264247B2 (en) 2015-02-27 2025-04-01 Cargill, Incorporated Rejuvenating compositions for asphalt applications and methods of manufacturing the same
US10316190B2 (en) 2015-02-27 2019-06-11 Cargill, Incorporated Polymerized oils and methods of manufacturing the same
US10329426B2 (en) 2015-02-27 2019-06-25 Cargill, Incorporated Rejuvenating compositions for asphalt applications and methods of manufacturing the same
EP3262083A4 (fr) * 2015-02-27 2018-07-25 Cargill, Incorporated Huiles polymérisées et leur procédés de fabrication
US11787945B2 (en) 2015-02-27 2023-10-17 Cargill, Incorporated Polymerized oils and methods of manufacturing the same
US12134699B2 (en) 2015-02-27 2024-11-05 Cargill, Incorporated Polymerized oils and methods of manufacturing the same
WO2016138407A1 (fr) 2015-02-27 2016-09-01 Cargill, Incorporated Huiles polymérisées et leur procédés de fabrication
US11905416B2 (en) 2015-02-27 2024-02-20 Cargill, Incorporated Polymerized oils and methods of manufacturing the same
US10316189B2 (en) 2015-02-27 2019-06-11 Cargill, Incorporated Polymerized oils and methods of manufacturing the same
US12122917B2 (en) 2015-02-27 2024-10-22 Cargill, Incorporated Polymerized oils and methods of manufacturing the same
US10316192B2 (en) 2017-08-25 2019-06-11 Cargill, Incorporated Emulsions with polymerized oils and methods of manufacturing the same
CN116925831A (zh) * 2022-11-30 2023-10-24 世名(苏州)新材料研究院有限公司 一种硫化烯烃及其制备方法和应用

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